Lipophilic Antioxidant

ABSTRACT

The present invention relates to a composition containing a first component selected from the group consisting of at least one polyphenol, at least one phenolic diterpene and mixtures of both, at least one glyceride, at least one hydrophilic emulsifier and at least one hydrophobic emulsifier, and also to the use of this mixture as lipophilic antioxidant.

The present invention relates to a composition containing a firstcomponent selected from the group consisting of at least one polyphenol,at least one phenolic diterpene and mixtures of both, at least oneglyceride, at least one hydrophilic emulsifier and at least onehydrophobic emulsifier, and also to the use of this mixture aslipophilic antioxidant.

Conventionally tocopherols and ascorbyl palmitate are used in order toprotect, for example, oils containing fatty acids having at least onedouble bond from oxidation.

Catechins are natural substances which occur in nature as plantcomponents. They are hydrogenated flavones. Catechins include, inparticular, catechin, epicatechin, gallocatechin and epigallocatechin.In the sense of the present invention, “catechin” or “a catechin” alwaysmeans a compound selected from the group of catechins. “Catechin” is notthe catechin meant in the narrow sense. If the catechin in the narrowsense is meant, then this will be also designated “catechin in thenarrow sense”. Catechins occur, for example, in green tea and can beextracted from this. Dried leaves of green tea can contain, for example,8.5 to 20.6% by weight of catechins. Information on catechins andcatechins in green tea may be found, e.g., in Renapp Online, Version3.0, published by Georg Thieme Verlag, under the headwords “Catechine”[Catechins] and “Tee” [Tea].

Catechins are active antioxidants and also have other beneficialproperties. However, catechins are hydrophilic and therefore cannotreadily be used as antioxidants in lipophilic media. It is thereforedesirable to make catechins available as antioxidants for lipophilicmedia.

Catechins are highly water soluble but very sparingly oil-solubleantioxidants. Recent scientific studies verify in additionhealth-promoting properties of catechins such as, e.g., accelerated fatcombustion, anticarcinogenic activity etc. The oil insolubilityrestricts the formulation ability of catechins to aqueous systems whichprevents their use as additives for oils or a mixture of oils.

In addition to catechins, polyphenols in general, in particular thosehaving antioxidant properties, are also usable as antioxidants. It istherefore desirable to be able to use not only catechins, butpolyphenols in general, as antioxidants in lipophilic media also.

If there were a way to incorporate polyphenols, in particular catechins,in a corresponding amount in a stable manner in oils, not only would thevery good antioxidant power of polyphenols be usable for oils, but alsothe health-promoting activity of polyphenols would be able to becombined with those of oils and/or oil formulations. Preferably, theformulations should be free from short-chain and medium-chain alcohols.

Diterpenes are natural substances having 20 carbon atoms which are madeup of four isoprene units. They belong to the terpene group. Compoundsdesignated diterpenes are not only hydrocarbons, but also derivatives ofthe corresponding hydrocarbons. Phenolic diterpenes are those diterpeneswhich contain at least one phenolic OH group. Carnosolic acid belongs tothe phenolic terpenes.

WO 94/22321 discloses solutions of catechins in nonionic solvents. Thesesolutions can be used as antioxidants in fats and oils. As solvents, inparticular nonionic surfactants are disclosed, in particular lecithinand fatty alcohols having 8-18 carbon atoms are disclosed. In example 7,inter alia, also glycerol monooleate is disclosed as solvent.

However, this has the disadvantage that catechins are only solubletherein at a low concentration and that frequently cloudy oils areobtained.

KR 2001079020 and JP-A 63135483 likewise disclose lipophilicantioxidants which contain catechins.

The object of the present invention was to provide substances which areusable as lipophilic antioxidants.

This object is achieved by a composition containing a first componentselected from the group consisting of at least one polyphenol (inparticular a polyphenol having antioxidant properties, preferably atleast one catechin), at least one phenolic diterpene (preferablycarnosolic acid) and mixtures of both, at least one glyceride, at leastone hydrophilic emulsifier and at least one hydrophobic emulsifier,wherein the hydrophilic emulsifier is selected from the group consistingof DATEM, CITREM, LACTEM, ACETEM and a sugar ester. This compositionaccording to the invention is subject matter of the present invention.

A particular embodiment of the present invention is the compositionaccording to the invention, wherein the first component is a catechin ora mixture of catechins and wherein this is preferably in the form of anextract of the leaves of green tea.

A further particular embodiment of the present invention is thecomposition according to the invention or one of the particularcompositions mentioned in the paragraphs hereinbefore, wherein the firstcomponent is a phenolic diterpene or a mixture of phenolic diterpenes,preferably carnosolic acid.

A further particular embodiment of the present invention is thecomposition according to the invention or one of the particularcompositions mentioned in the paragraphs hereinbefore, wherein theglyceride is a triglyceride, the three fatty acids of which each have 6to 18 carbon atoms.

A further particular embodiment of the present invention is thecomposition according to the invention or one of the particularcompositions mentioned in the paragraphs hereinbefore, wherein thehydrophilic emulsifier is selected from the group consisting of DATEM,CITREM, LACTEM and ACETEM.

A further particular embodiment of the present invention is thecomposition according to the invention or one of the compositionsmentioned in the paragraphs hereinbefore, wherein the hydrophilicemulsifier is a sugar ester.

A further particular embodiment of the present invention is thecomposition according to the invention or one of the particularcompositions mentioned in the paragraphs hereinbefore, wherein thehydrophobic emulsifier is selected from the group consisting of apolyglycerol polyricinoleate, a polyglycerol ester of fatty acid andglycerol monoester of fatty acid (i.e. a monoglyceride; in particularsuch a monoglyceride having a fatty acid having 10 to 30 carbon atoms,in particular glycerol monooleate or glycerol monostearate).

A further particular embodiment of the present invention is thecomposition according to the invention or one of the particularcompositions mentioned in the paragraphs hereinbefore, additionallycontaining water.

A further particular embodiment of the present invention is thecomposition according to the invention or one of the particularcompositions mentioned in the paragraphs hereinbefore, containing 1 to20% by weight, in particular 5 to 15% by weight, of the first component,2 to 70% by weight, in particular 20 to 50% by weight of glyceride, 3 to60% by weight, in particular 15 to 35% by weight of hydrophilicemulsifier, 3 to 60% by weight, in particular 15 to 35% by weight, ofhydrophobic emulsifier and 0 to 30% by weight, in particular 0 to 1% byweight, of water.

The present invention further relates to a process for producing thecomposition according to the invention or one of the compositionsmentioned in the paragraphs hereinbefore which comprises providing amixture containing the hydrophilic emulsifier and the hydrophobicemulsifier, optionally warming this mixture to a temperature of at least50° C., adding the first component to this mixture (optionally withstirring) and thereafter adding the glyceride.

The present invention further relates to a use of the compositionaccording to the invention or of one of the particular compositionsmentioned in the paragraphs hereinbefore as antioxidant for lipophilicmedia, wherein the lipophilic medium preferably contains an oil or fatand in particular is a food.

The present invention further relates to a second composition containingoil or fat and, based on the mass of the oil or fat, 0.05 to 3% byweight of the composition according to the invention or of one of theparticular compositions mentioned in the paragraphs hereinbefore.

A further particular embodiment of the present invention is said secondcomposition, wherein the oil or fat is selected from the groupconsisting of a fat or oil which contains unsaturated fatty acidradicals (in particular radicals of linoleic acid, linolenic acid oroleic acid), fish oil, sunflower oil, borage oil, a glyceride whichcontains acyl radicals of conjugated linoleic acid and a triglyceride,the acyl radicals of which have 6 to 24 carbon atoms.

A further particular embodiment of the present invention is the secondcomposition according to any of the paragraphs hereinbefore, wherein thesecond composition is an oil-in-water emulsion.

A further particular embodiment of the present invention is the secondcomposition according to any of the paragraphs hereinbefore, wherein thesecond composition is granules or a powder.

Powders for the purposes of the present invention are also all furtherformulations having a solids character, such as, e.g., granules.

A further particular embodiment of the present invention is the secondcomposition according to any of the paragraphs hereinbefore, wherein thesecond composition is a food, in particular one such selected from thegroup consisting of an oil, a fat, olive oil, butter, margarine, milk, amilk product, cheese, yogurt, a chocolate bar and a muesli bar.

According to the present invention the hydrophilic emulsifier can beselected, in particular, from the group consisting of DATEM, CITREM,LACTEM and ACETEM. In this case DATEM is a composition of mattercontaining mono- and diacetyl tartaric esters of mono- and diglyceridesof edible fatty acids, in particular DATEM is a composition of matterwhich contains substituted glycerol molecules which are esterified at atleast two OH groups and which bear at least one fatty acid radical (morethan 50 mol % of the fatty acid radicals have 16 or 18 carbon atoms) andwhich bear at least one tartaric acid radical which in turn ismonoacetylated or diacetylated. CITREM is a composition of mattercontaining citric esters of mono- and diglycerides of edible fattyacids. LACTEM is a composition of matter containing lactic esters ofmono- and diglycerides of edible fatty acids. ACETEM is a composition ofmatter containing acetic esters of mono- and diglycerides of ediblefatty acids. Edible fatty acids have, in particular, 6 to 24 carbonatoms.

A hydrophobic emulsifier has an HLB value of less than 8, a hydrophilicemulsifier has an HLB value of at least 8. The HLB value can bedetermined for nonionic emulsifiers in accordance with Griffin, and forionic emulsifiers in accordance with Davies. For determination of HLBvalues see: Tensid-Taschenbuch [Surfactant Handbook], 2nd edition,edited by H. Stache, Carl Hanser Verlag, 1981.

The designation PGPR (polyglycerol polyricinoleate) summarizes esters ofpolycondensed castor oil fatty acids with polycondensed glycerol.Ricinoleic acid is 12-hydroxyoleic acid and can form a polyester withitself. Esters of polycondensed castor oil fatty acids withpolycondensed glycerol are permitted as a food additive in Germany underthe designation E 476. Polyglycerol fatty acid esters can, for example,have the composition of the commercial product Polymuls® 2G from CognisGmbH, Monheim, Germany. This is a mixture of (% in each case is % byweight) fatty acid monoesters of diglycerol: 65-75%, fatty acidmonoesters of glycerol: 15-20%, fatty acid diesters of glycerol: 5-10%,total glycerols: 30-40%, free glycerols: 2-5%.

A sugar ester for the purposes of the present invention is, inparticular, an ester of a molecule of a sugar selected from the groupconsisting of sucrose, fructose, glucose and trehalose (sucrose ispreferred) and one to three molecules of edible fatty acid (preferably afatty acid having 6 to 24 carbon atoms).

A glyceride for the purposes of the present invention is an ester ofglycerol with 1, 2 or 3 fatty acids. A monoglyceride here is an ester ofglycerol with one fatty acid, a diglyceride is an ester of glycerol withtwo fatty acids and a triglyceride is an ester of glycerol with threefatty acids. Fatty acids in this case are preferably carboxylic acidshaving 2 to 30, in particular 2 to 20, in particular 6 to 18, inparticular 8 to 10, carbon atoms. Triglycerides are glycerides which arepreferred according to the invention.

CLA is an abbreviation for conjugated linoleic acid, that is for anoctadecadienoic acid, wherein the two double bonds are not separated byone or more saturated carbon atoms, but start at carbon atoms no. n andn+2 (n is a natural number from 2 to 15). Preferably, the double bondsare situated either at positions 9 and 11 (9,11-octadecadienoic acid) orat positions 10 and 12 (10,12-octadecadienoic acid). In this case,cis-trans isomerism (E-Z isomerism) is possible at each double bond. Theisomers possible for CLA are designated by the symbols c for cis and tfor trans and by quoting the numbers for the position of the doublebonds, that is to say, e.g., c9,t11-CLA. In a preferred embodiment ofthe present invention, CLA is c9,t11-CLA or t10,c12-CLA.

The composition according to the invention has numerous advantages overthe prior art. The composition according to the invention must containno alcohols. It must not contain glycerol monooleate; this isadvantageous in some cases, since glycerol monooleate in some cases hasa tendency to form β-phases which can become noticeable as unwanteddeposits in formulations. For β-phases in glycerol monooleate, see“Emulgatoren für Lebensmittel” [Emulsifiers for Foods], published byGregor Schuster, Springer-Verlag, 1985, pages 82 to 87.

All example formulations in WO 94/22321 contain the catechin only in aconcentration of 2.7% by weight. The compositions according to theinvention can have a catechin content which is up to approximately fourtimes higher. That means approximately four times less (frequentlyundesired) auxiliaries are also introduced into the final formulation(at comparable catechin concentrations in the end formulation). Inaddition, the compositions according to the invention are flexible to acertain extent in the choice of glyceride (auxiliary oil). Fish oil, forexample, can be used as such. The introduction of auxiliary into the endformulation can be reduced still further.

The composition according to the invention exhibits a significantlybetter antioxidant activity than conventional antioxidants. The verygood antioxidant activity leads to an improved long-term stability andimproved sensory stability of the stabilized products.

The products stabilized by the composition according to the inventionhave good sensory properties. For instance, they do not have, e.g., anunpleasant bitter taste as is the case with, e.g., the emulsifierpolysorbate 60 (commercially available as Tween 60).

The composition according to the invention does not require any alcoholsand may be formulated not only with water but also without water. Thewater-containing concentrates then, after dissolution in oil, preferablygive a W/O microemulsion. The antioxidant activity of the compositionaccording to the invention surpasses that of the conventionaloil-soluble antioxidants at comparable concentration manyfold. This isconfirmed by the stability tests which are conventional for unsaturatedoils such as the Rancimat test and determination of the peroxide value.

The composition according to the invention may be incorporated into themost varied triglycerides such as, e.g., fish oils, sunflower oil,conjugated linoleic acids and medium-chain triglycerides, which enablestheir use in numerous foods and food supplements.

The resultant solutions generally show either no additional turbidityor, at higher concentrations, a slight additional turbidity of the oil(compared with the oil without composition according to the invention).

The production and introduction of the composition according to theinvention into lipophilic media which are to be protected againstoxidation can be illustrated schematically and for an exampleformulation as follows: dissolve, e.g., a green tea extract in water;glycerol monooleate and tartaric esters are heated with stirring (50°C.); the green tea extract/water mixture is stirred into the glycerolmonooleate/tartaric ester mixture, thereafter a short-chain triglycerideis added. The resultant water can if required be removed (e.g. by freezedrying). The composition according to the invention is (preferablywithout heating) stirred into the corresponding oil phase or fat phase.The amount of composition which is stirred in depends on the use. If thecomposition principally acts as antioxidant, the amount is calculated insuch a manner that the concentration of the composition in the final oilformulation or fat formulation is in the range 500-1000 ppm (coarseguide value). With other applications the concentrations arecorrespondingly higher.

The composition according to the invention contains, as auxiliary forsolubilization, a mixture of hydrophilic and hydrophobic emulsifiers,and preferably also an auxiliary oil. The hydrophilic emulsifier ispreferably the tartaric ester of mono- and diglycerides, the hydrophobicemulsifier preferably glycerol monooleate. As auxiliary oil, preferably,medium-chain triglyceride (C8/C10 triglyceride) is used.

For production of the composition according to the invention, first,preferably, a water-containing concentrate is produced, since this has abetter absorption capacity for the first component than thecorresponding water-free mixture. The water can, if required, be removedagain (e.g. by freeze drying). The water-free concentrates especiallyhave a tendency to give a clear solution in oil.

Typical example compositions contain the components in the followingquantitative ranges (all figures in percent by mass):

Green tea extract  5-20% (contains approximately 70% catechins) Glycerolmonooleate 10-35% Tartaric esters 10-35% C8/C10 triglyceride 10-50%Water  0-10%

The compositions according to the invention are preferably introducedinto the second compositions according to the invention atconcentrations such that the first component of the compositionaccording to the invention, based on the oil or fat in the secondcomposition, is present in a concentration of 20 to 1000 ppm, preferably30-500 ppm, particularly preferably 30-300 ppm.

The second composition according to the invention can be, in particular,a food.

EXAMPLES

In the examples, proprietary products were used which were all obtainedfrom Cognis GmbH, Monheim, in Germany, unless stated otherwise. Thetable hereinafter compares the brand names and the chemical compositionof the products used.

Brand name Chemical composition Polymuls ® PGPR a polyglycerolpolyricinoleate Polymuls ® 2G a fatty ester polyglycerol Monomuls ®90-O18 glycerol monooleate Delios ® V a triglyceride, the fatty acids ofwhich have predominantly 8 or 10 carbons atoms Lamegin ® DWP 2000 anemulsifier which is one of what are termed DATEM (diacetyl tartaricester monoglycerides); this is a composition of matter which containsglycerol molecules which are esterified at at least two OH groups, andwhich bear at least one fatty acid radical (chain length of the fattyacid radicals: predominantly 16 and 18 carbon atoms) and which bear atleast one tartaric acid radical which in turn is monoacetylated ordiacetylated. Coviox ® T 90 EU natural tocopherols Hi Cap 100 1-octenylsuccinic anhydride- esterified (OSA) starch

All percentage figures in the examples are percent by weight, unlessstated otherwise.

The following compositions were produced:

First Hydrophilic Hydrophobic No. component Glyceride emulsifieremulsifier 1 Catechin solution 37.5% 25% 25% (72.73% green Delios ® VLamegin ® Monomuls ® tea powder + DWP 2000 90-O18 27.27% water): 12.5% 2Catechin solution 30% 25% 25% (72.73% green Delios ® V Lamegin ®Monomuls ® tea powder + DWP 2000 90-O18 27.27% water): 20% 3 Catechinsolution 30% 25% 22.73% (72.73% green Delios ® V Lamegin ® Polymuls ®tea powder + DWP 2000 PGPR and 27.27% water): 2.27% 20% Polymuls ® 2G 4Catechin solution 30% 25% 25% (72.73% green Delios ® V Lamegin ®Polymuls ® tea powder + DWP 2000 PGPR 27.27% water): 20% 5* 9.1% GreenTea 37.5% 25% 25% Low Caffeine Dry Delios ® V Lamegin ® Monomuls ®Extract DWP 2000 90-O18 (contained approximately 70% catechins) 6* 9.4%Green Tea 38.8% 25.9% 25.9% Low Caffeine Dry Delios ® V Lamegin ®Monomuls ® Extract DWP 2000 90-O18 (contained approximately 70%catechins) *Composition No. 6 was obtained by removing the water fromcomposition No. 5. Composition No. 5 contained 3.4% water.

Production of a Polyphenol Mixture Based on Catechin

25 g of Monomuls® 90-O18 and 25 g of Lamegin® DWP 2000 were warmed toapproximately 50° C. and mixed and melted with stirring. Subsequently12.5 g of a catechin mixture consisting of “green tea low caffeine dryextract” (caffeine: 0.33%; epigallocatechin gallate: 42.7%; catechins intotal: 70.46%) and water were stirred into the emulsifier premix. Afterhomogeneous distribution, 37.5 g of MCT (Delios® V) were added.Subsequently the water was removed by freeze drying.

Production of the Catechin-Containing Fish Oil

The above-described polyphenol mixture based on catechin was stirredinto fish oil:

-   -   0.76 g of the polyphenol mixture based on catechin in 99.24 g of        fish oil 18/12: concentration therefore 500 ppm    -   1.52 g of the polyphenol mixture based on catechin in 98.48 g of        fish oil 18/12 concentration therefore 1000 ppm.

Fish oil 18/12 is fish oil containing 18% EPA (eicosapentaenoic acid)and 12% DHA (docosahexaenoic acid)

The table hereinafter makes clear the stabilizing activity of catechincompared with conventional antioxidants and mixtures thereof based onthe induction periods (as a measure of oxidative stability) determinedusing the Rancimeter.

Rancimat method for measuring oxidation stability:

In the Rancimat method, the sample is exposed to an airstream attemperatures of 50-220° C. The high-volatility oxidation products (themajority formic acid) are transferred by the airstream into themeasurement vessel and there absorbed in the measurement solution(distilled water). In continuous recording of the conductivity of thismeasurement solution, oxidation curves are obtained, the inflectionpoint of which is designated induction time, and is a goodcharacteristic value for oxidation stability. The Rancimat method wasdeveloped as an automated variant of the extremely complex active oxygenmethod (AOM) for determining the induction time of fats and oils. In thecourse of time, the method has established itself and found use invarious national and international standards, for example AOCS Cd 12b-92and ISO 6886.

TABLE Rancimat test of fish oil 18/12 Induction Antioxidant period Notstabilized 1.08 h 4400 ppm Coviox ® T 90 EU 2.50 h 4400 ppm Coviox ® T90 EU + 500 ppm 4.30 h ascorbylpalmitate 500 ppm catechin 10.8 h 1000ppm catechin 16.0 h

Conditions: 5 g at 120° C. with 20 l of air per hour

Production of a catechin-containing fish oil powder

The catechin mixture described hereinbefore was stirred into the fishoil in an appropriate amount. The catechin-containing oil was mixed withthe water phase and corresponding amounts of emulsification aids andhomogenized.

The resultant emulsion was then freed from the water by a suitableprocess (e.g. spray-drying) so as to arrive at a powder/granules.

Example of a Formulation for Removal of the Water

Mass/g Fish oil 18/12 50.00 Na Caseinate 10.00 Glucose DE 29 24.00 HiCap 100 6.00 Soya protein 10.00 Antioxidant catechin (1000 ppm catechinin oil) Water 150.0

Uses of the Catechin-Containing Fish Oil Powder in Milk Products

Incorporation of 2.67 g of the powder hereinbefore in 150 ml of milk(optionally with subsequent pasteurization)

Incorporation of 2.67 g of the powder hereinbefore into 150 ml ofyogurt. The incorporation can proceed

a) by using the abovementioned fish oil-containing milk, which is thenprocessed by a corresponding fermentation process to give a yogurt or

b) by adding the powder directly into the yogurt or via the fruit phaseinto a yogurt.

Use of a Polyphenol-Containing Fish Oil Powder in a Bar

Example formula of a fish oil-containing cereal bar. Fish oil or fishoil powder contained the amounts of catechin mentioned in exampleshereinbefore.

Composition [%] Fish oil powder (15% PUFA) 1.90 Sugar 12.15 Glucosesyrup solid 18.90 Sorbitol (powder) 2.70 Water 11.25 Sunflower oil 4.85Lecithin (liquid) 0.15 Cornflakes 19.90 Oat flakes 8.10 Wheat flakes8.10 Raisins (sultanas) 10.50 Banana chips 1.20 Apple pieces 0.30 Total100.00

Production of the B

Step 1: Production of the syrup mixture:

mix 12.5 g of sugar, 18.9 g of glucose syrup, 2.7 g of sorbitan powderand 11.25 g of water and heat it to approximately 60° C.

Step 2: Production of the fat mixture:

mix 4.85 g of sunflower oil and 0.15 g of lecithin and heat toapproximately 60° C.

Step 3: Add the fat mixture to the syrup mixture and heat the mixture to90-95° C.

Step 4: Production of the cereal mixture:

mix 1.90 g of fish oil powder with the cereals and optionally withfurther components (such as flavorings/aroma substances, vitamins,minerals). Alternatively, the fish oil (powder or oil) can be addeddirectly to the fat mixture.

Step 5: Add the cereal mixture to the syrup mixture

Step 6: Feed to the roller compacter

Step 7: Cooling and cutting of the bars

Further Examples

% always means percent by weight.

The following further examples relate to PUFA emulsions(PUFA=polyunsaturated fatty acid) stabilized with phenols and/orpolyphenols. These are water-in-oil emulsions of PUFA-containing oils orfats, e.g. fish oil.

These emulsions display significantly better sensory properties andoxidative stability than conventionally stabilized emulsions, even afterthermal stress such as, e.g., pasteurization.

An o/w emulsion was produced using a high-pressure homogenizer andemulsification aids (emulsifiers). The oil-soluble components arecharged for this in the oil phase, the water-soluble components in thewater phase.

A heating of the phases can accelerate the solution process. The twophases are combined and homogenized using the homogenizer. Addition ofthe phenols/polyphenols proceeds, according to their solubility, eitherto the water phase or oil phase. In the case of carnosolic acid,addition is via the oil phase, in the case of catechin the addition isvia the water phase or, if the catechin was appropriately preformulated,also via the oil phase.

A typical formulation is the following:

-   -   40-60% fish oil (Omevital® 18/12 TG Gold, obtainable from Cognis        GmbH, Monheim, Germany)    -   0.5-10% modified starch (Hi-Cap 100, obtainable from National        Starch)    -   0.5-10% whey protein hydrolysate    -   pH regulators such as lactic acid and/or citric acid    -   content of phenols/polyphenols (including the corresponding        esters) of 20-1000 ppm, preferably 30-500 ppm, particularly        preferably 30-300 ppm, based on the oil phase or water phase    -   remainder: water

A further typical formulation is the following:

-   -   40-60% fish oil (Omevital® 18/12 TG Gold, Cognis)    -   0.5-10% sucrose ester (Sisterna SP 70, Sisterna)    -   0.5-10% lecithin (rapeseed lecithin)    -   0-10% whey protein hydrolysate    -   pH regulators such as lactic acid and/or citric acid preferred    -   content of phenols/polyphenols (including the corresponding        esters) of 20-1000 ppm, preferably 30-500 ppm, particularly        preferably 30-300 ppm, based on the oil phase or water phase    -   remainder: water

The viscosity of the emulsions is below 5000 mPas, preferably below 3000mPas, particularly preferably below 1500 mPas.

A trained test panel rated the PUFA emulsions stabilized withphenols/polyphenols as superior compared with non-stabilized emulsionsor emulsions stabilized in a conventional manner.

Advantage: high sensory and oxidative stability. Even after thermalstress such as pasteurization.

These emulsions can be used in the following food matrices:

-   -   dairy products (milk, yogurt, drinking yogurt, cheese etc.)    -   drinks in general    -   milk-based fruit drinks and soft drinks    -   soya-based fruit drinks and soft drinks    -   liquid food supplements

These emulsions can be produced as follows:

-   -   charge deionized water into stirring equipment    -   stir in HI-CAP emulsifier at RT    -   heat to 80-85° C. (duration 10 min), at approximately 60° C. add        whey protein concentrate    -   hold for 10 min (heating step)    -   cool to 15-20° C. (duration 15 min)    -   dissolve antioxidant in subquantity of fish oil or water, added    -   add fish oil    -   adjust with anhydrous citric acid to pH 4.0    -   stirred for 5 min (emulsification)    -   homogenized 1×at a pressure of 230/30 bar,    -   viscosity: 240 mPas    -   pasteurization (optional)    -   emulsion of experiment 1 heated to 80° C. in the water bath in        100 ml square bottles, duration approximately 15 min    -   heated for 5 minutes further, 85° C.    -   bottles removed from water bath, placed turned over into the        refrigerator    -   viscosity: 210 mPas (pasteurized)

Further formulation examples:

A 500 g Omevital ® 18/12 TG Gold 30 g modified starch HI-CAP 100 450 gwater 20 g whey protein hydrolysate 2 g anhydrous citric acid 125 mgcatechin (=250 ppm based on water phase) B 500 g Omevital ® 18/12 TGGold 30 g modified starch HI-CAP 100 450 g water 20 g whey proteinhydrolysate 2 g anhydrous citric acid 125 mg carnosolic acid (=250 ppmbased on oil phase) C 500 g Omevital ® 18/12 TG Gold 30 g modifiedstarch HI-CAP 100 450 g water 20 g whey protein hydrolysate 2 ganhydrous citric acid 62.5 mg catechin (=125 ppm based on water phase)62.5 mg carnosolic acid (=125 ppm based on oil phase)

Example D: Use of the emulsion in milk

1 g of emulsion from the above example is added to 99 g of milk (fatcontent 1.5%) with stirring. Optionally, pasteurization can proceedthereafter.

Example C: Use of the emulsion in yogurt

The product according to Example A was added according to Example D tomilk. After homogenization at 200 bar, the milk was cooled to 45° C. 50g of bacterial starter culture for yogurt (YC 180 from Chr. Hansen) wereadded to 450 g of the milk dispersion. For the fermentation, varioussamples were placed in an incubator at 45° C. After reaching a pH of 4.5to 4.6, the samples were cooled, 7% sugar was added with stirring (toobtain a stirred yogurt) or they were homogenized at 80 to 100 bar (toobtain a drinking yogurt).

1.-10. (canceled)
 11. A composition comprising: (a) 1 -20% of a firstcomponent selected from the group consisting of at least one polyphenol,at least one phenolic diterpene and combinations thereof, (b) 2-20% ofleast one glyceride, (c) 3-60% of least one hydrophilic emulsifier, and(d) 3-60% at least one hydrophobic emulsifier, and (e) 0-30% waterwherein the hydrophilic emulsifier is selected from the group consistingof mono- and diacetyl tartaric mono- and diglycerides of edible fattyacids, citric mono- and diglycerides of edible fatty acids, lactic mono-and diglycerides of edible fatty acids, acetic mono- and diglycerides ofedible fatty acids and sugar esters.
 12. The composition of claim 11,wherein component (a) is catechin or a mixture of catechins.
 13. Thecomposition of claim 11, wherein component (a) is carnosolic acid. 14.The composition of claim 11, which comprises 15 to 35% by weight of thehydrophilic emulsifier, and 15 to 35% by weight of the hydrophobicemulsifier.
 15. The composition of claim 11, wherein the hydrophilicemulsifier is a sugar ester.
 16. The composition of claim 11, whereinthe hydrophobic emulsifier is selected from the group consisting ofpolyglycerol polyricinoleates, polyglycerol esters of fatty acids, andglycerol monoesters of fatty acids.
 17. The composition of claim 16,wherein said hydrophobic emulsifier is a monoglyceride of a fatty acidhaving about 10 to about 30 carbon atoms.
 18. The composition of claim16, wherein said hydrophobic emulsifier is selected from the groupconsisting of glycerol monooleate and glycerol monostearate.
 19. Aprocess for producing the composition of claim 11 which comprises: (i)providing a mixture containing the hydrophilic emulsifier (c) and thehydrophobic emulsifier (d); (ii) adding component (a) to this mixture;and (iii) thereafter adding the glyceride component (b).
 20. Acomposition comprising: (a) at least one oil or fat; and (b) about 0.05to 3% by weight of the composition of claim 11, based on the weight ofthe at least one oil or fat.
 21. The composition of claim 20, whereinthe oil or fat is selected from the group consisting of fats and oilswhich contain unsaturated fatty acid moieties, fish oil, sunflower oil,borage oil, glycerides which contain acyl moieties of conjugatedlinoleic acid, and triglycerides having acyl moieties of 6 to 24 carbonatoms.
 22. A method for improving the oxidation stability of lipophilicmedia comprising adding the composition of claim 11 to the lipophilicmedium in an amount effective to improve the oxidation resistance oversaid medium without the added composition.